Detergent compositions

ABSTRACT

DETERGENT COMPOSITION COMPRISING (A) FROM 20 TO 90 WT. PERCENT OF AT LEAST ONE SURFACTANT SELECTED FROM THE GROUP OF ANIONIC, ZWITTERIONIC AND NON-IONIC SURFACTANCTS, AND (B) FROM 10 TO 80 WT. PERCENT OF, AS TEXTILE SOFTENER, AN N-ALKYL-N-ACYL-N-POLYHYDROXALKYL COMPOUND OF THE FORMULA:   R1-N(-Z)-CO-R2   WHEREIN R1 IS ALKYL HAVING 10 TO 22 CARBON ATOMS, WHICH CAN BE INTERRUPTED BY AN ETHER OXYGEN IN THE VICINITY OF THE NITOGEN ATOMS R2 IS ALKYL HAVING 7 TO 21 CARBON ATOMS, R1 AND R2 TOGETHER CONTAINING FROM 23 TO 39 CARBON ATOMS AND Z IS A POLYHYDROXALKYL HAVING ONE OF THE FOLLOWING FORMULAE:   -CH2-(CH(-OH))M-CH2-OH AND -CH(-CH2-OH)-(CH(-OH))N -CH2-OH   WHEREIN M HAS A VALUE OF 3 OR 4 AND N HAS A VALUE OF 2 TO 3.

3,654,166 DETERGENT COMPOSITIONS Hans-Werner Eckert, Dusseldorf, andArnold Heins, Hilden, Rhineland, Germany, assignors to Henkel & CieGmbH, Dusseldorf, Postfach, Germany No Drawing. Continuation-impart ofapplication Ser. No. 656,136, July 26, 1967. This application Aug. 2,1968, Ser. No. 749,596 Claims priority, application Germany, Aug. 14,1967, H 63,601; May 8, 1968,P 17 67 413.4 The portion of the term of thepatent subsequent to Jan. 25, 1989, has been disclaimed Int. Cl. 011d3/30; D06m 13/38, 13/40 US. Cl. 252-117 9 Claims ABSTRACT OF THEDISCLOSURE Detergent compositions comprising (a) from 20 to 90 wt.percent of at least one surfactant selected from the group of anionic,zwitterionic and non-ionic surfactants, and (b) from 10 to 80 wt.percent of, as textile softener, an N-alkyl-N-acyl-N-polyhydroxyalkylcompound of the formula:

wherein R is alkyl having 10 to 22 carbon atoms, which can beinterrupted by an ether oxygen in the vicinity of the nitrogen atom, Ris alkyl having 7 to 21 carbon atoms, R, and R together containing from23 to 39 carbon atoms and Z is a polyhydroxyalkyl having one of thefollowing formulae:

( I) CHZOH 2- I J} 011-- HOH)m and I (011011) HzOH H2OH wherein in has avalue of 3 or 4 and n has a value of 2 or 3.

RELATED APPLICATION AND TERMINAL DISCLAIMER This application is acontinuation-in-part of Ser. No. 656,136, filed July 26, 1967, by thepresent inventors. The terminal portion of the life of any patent, basedon the present application, extending beyond the life of any patentbased on Ser. No. 656,136, is hereby disclaimed.

The compositions of the invention are detergents and represent novelcombinations of wash active surfactants and textile softening agents.

The present invention relates to detergent compositions. Moreparticularly, this invention relates to detergent compositionscontaining wash-active and textile softening agents.

Following the drying, mechanically or otherwise, of washed textiles,particularly those prepared from cotton and similar cellulose fibers, aperceptible hardening of the feel thereof can be detected. This isespecially true where these textiles have been washed in drum-typewashing machines. This phenomenon is particularly unpleasant inconnection with articles of clothing which in their u'se come in contactwith the human skin, as for example, in undergarments and in the case ofbedding and handkerchieis. It is also true regarding otherconventionally laundering items such as table linens, in connection withwhich a pleasant feel is considered highly desirable.

This undesirable hardening of the feel can be prevented in thelaundering process by adding to the final rinse, cationic substanceswhich contain at least two fatty "United States Patent 3,654,166Patented Apr. 4, 1972 ice radicals of high molecular weight in theirmolecules. In practice, dialkyl dimethyl ammonium salts which can besuspended in water have been introduced in the form of so-called rinsingagents for this purpose. Since these cationic textile softeners formwater-insoluble precipitates with the anionic wash-active substances,they cannot be added to the detergent itself. However, even when theyare used in the final rinse, precipitates can be formed between theresidues of anionic wash-active substances that remain in the rinsewater or on the fibers of the washed textiles, and the cationic textilesofteners.

Heretofore no detergent composition has been known which contained atextile softening agent that was compatible with the anionic wash-activeagents.

In -accordance with the invention it has now been found that when ananionic and/or hybrid-ionic and/or non-ionic surfactant is mixed with atextile softening agent, the resulting mixture can be used as a textiledetergent. The compositions of the invention are mixtures containing:

(a) from 20 to 90% by weight, preferably 30-70% by weight, of asurfactant of the above-named types, and

(b) from 10 to by weight and preferably 30 to 70% by Weight, of anN-al'kyl-vN-acyl-N-polyhydroxyalkyl compounds as textile softener,having the formula R IIIC 0-R,

in which:

R, is alkyl having 10 to 22, preferably 12 to 20, and most preferably 16to 18 carbon atoms; wherein said alkyl can be interrupted by an etheroxygen atom in the vicinity of the nitrogen atom,

R is alkyl having 7 to 21, preferably 11 to 19, and most preferably 15to 17 carbon atoms; R and R together having a total of 23 to 39, andpreferably 27 to 35 carbon atoms, and

Z is polyhydroxyalkyl having one of the following formulae:

CH CH OH JHOEDm and H- H OH IHOH)n JHZOH wherein in has a value of 3 or4 and n has a value of 2 or 3. (The polyhydroxyalkyl groups Z may beattached etherally to other polyhydroxyalkyl groups.)

Of particular practical importance are those compounds in which m is 4and n is 3, i.e., derivatives of the glycamines. (These glycamines willbe referred to hereinafter as glycamides.) Compounds wherein m is 3 andn is 2 are also suitable for use herein and can be substitutedadvantageously for the so-called glycamides.

The invention furthermore relates to dry, pasty or liquid detergentcompositions and other washing aids containing the abovesurfactant-softener combinations and containing in addition the otherconventional detergent components, the surfactant-softener combinationamounting to from 5 to 80 and preferably 15 to 40% by weight, and theadditional conventional detergent components amounting to from 20 to 95and preferably from to 60% by weight of the resulting composition.

The conventional detergent components which can be present include, forexample, neutral to alkaline reacting builder substances, complexformers, bleaching components, suds stabilizers, suds inhibitors anddirt carriers.

The invention additionally relates to Surfactant-textile softenercombinations usable as textile deterents, as well as detergentcompositions or washing adjuvants containing such surfactant-textilesoftener combinations which are characterized by a content of enzymes.

Instances of suitable enzymes include the proteases, amyla-ses, whichcan be incorporated into the compositions according to the inventioneither singly or in any combination. If the products are detergentcompositions or washing adjuvants, the protease content can correspondto activities of 50 to 5000, and preferably 100 to 2500 LVE/ g., theiramylase content can correspond to activities of 20 to 5000, preferably50 to 2000 SKBE/g, and their lipase content to activities of 2 to 1000,preferably from 5 to 500 IE per gram of detergent or Washing adjuvant.

If the compositions according to the invention are surfactant-textilesoftener combinations as are often used in industrial laundries incombination with conventional builder materials, the enzyme content ofsuch compositions should be regulated so that the preparation composedof the surfactant-textile softener combination toether with the othercomponents of the detergent or washing aid are of the enzyme contentstated above. As the surfactanttextile softener combination can amountto from 5 to 80%, and preferably from to 40% of the total detergentcomposition or of the washing aid, the enzyme activities for thesurfactant-textile softener combinations are calculated at 62.5 to100,000 LVIE for proteases, 25 to 100,000 SKBE for amylases, and 2.5 to20,000 IE for lipases, per gram of surfactant-textile softenercombination. Surfactant-textile softener combinations having activitiesclose to the upper limits can be produced only if very active enzymepreparations are available. This is why the maximum activities areusually around 50,000 LVE, 50,000 SKBE and 10,000 IE per gram ofsurfactant combination. The enzyme activities preferably range from 250to 15,000 LVE, 125 to 15,000 SKBE and 12.5 to 3,500 IE per gram ofsurfactant combination.

The above data on the enzyme contents and activities of the preparationsaccording to the invention are based on the activities of those enzymepreparations which, on the date of filing, appeared to be usuable in thedetergent field from the economic viewpoint. From the chemicalstandpoint, the enzyme activities of the preparations according to theinvention can be increased as needed, so that the activities in the caseof proteases and amylases can be increased up to 5 times, and in thecase of lipases up to 10 times, the maximums stated above. If,therefore, enzyme preparations having higher contents of active enzymeshould be made available in the future, which appear to be suitable foruse in the detergent field from the economic viewpoint, the option ofkeeping the enzyme activity of the preparation at the above-stated levelusing smaller quantities of enzyme, or of increasing the enzyme activityusing the same quantity of enzyme is presented.

Reference is made of the following literature in regard to determiningenzyme activities:

Determination of activity of proteases by the method of Lohlein-Volhard:A. Kunzel: Gerbereichemisches T aschenbuch, 6th ed., Dresden andLeipzig, 1955 Determination of activity of amylases: I. Wohlgemuth:Biochernische Zeitschrift, vol. 9 (1908), pp. 1-9, and

'R. M. Sandstedt, E. Kneen and M. J. Blish: Cereal Chemistry, vol. 16(1939), pp. 712-723 Determination of activity of lipases: R.Willstatter, 'Waldschmidt-Leitz and Fr. Memmen: Hoppe-SeylersZeitschrift fur Physioloische Chemie, vol. 125 (1923), pp. 110117, andR. Boissonas: Helvetia Chimica Acta, vol. 31 (1948), pp. 1571-1576.

The glycamides suitable for use in formulating the mixtures inaccordance with the invention can be produced by amidation in the knownmanner from the corresponding glycamines which are obtained by thehydrogenation of hexoses or oligomers thereof using Raney nickel and inthe presence of higher alkylamines.

The hexoses employed in the hydrogenation are preferably monosacchardiessuch as glucose, mannose, galactose, fructose, sorbose or mixturesthereof, such as invert sugar. However, the oligomers thereof can alsobe used, such as, for example, maltose. Pentoses or pentose mixtures canbe process in the same manner, in which case, compounds in which in is 3and n is 2 are obtained, the same also being suitable for use as thetextile softening agent. Mixtures of pentoses and hexoses can also beadvantageously used.

The alkyl radicals of the amines which are used in the preparation ofthe textile softeners according to the invention can be similar to theradicals of the amidally bonded fatty acids, saturated or unsaturated,straight-chained or branched, and of synthetic or natural origin.Accordingly, the radicals R can be derived from decylamine, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, arachylamineor behenylamine. The carbon chains of these alkyl radicals may also beinterrupted by ether oxygen atoms in the vicinity of the nitrogen atomand preferably between carbon atoms 2 and 3 or 3 and 4, respectively(counting from the nitrogen atom).

The fatty acid radicals R -CO- can be derived from capric, lauric,myristic, palmitic, stearic, oleic, arachinic or behenic acid. Since theamines used for the preparation of the textile softeners are obtainablefrom the corresponding fatty acids through the amides or nitriles, boththe alkyl amines and the fatty acid radicals may be 'in the form ofhomologous mixtures, as they are found, for example, in fats of naturalorigin. Accordingly, the radicals R and R CO- can be prepared from fatsderived from plant, marine or land animal sources. They can be obtained,for example, from coconut oil, palm oil linseed oil, cottonseed oil,peanut oil, rape oil etc. hog lard, tallow, fish oil, whale oil or fromfractions of the fatty acids contained in these fats and oils. Theaforesaid radicals are preferably to be of a substantially saturatednature.

The invention is of particular practical importance in connection withthe so-called complete detergents, i.e., the detergents that are used inthe main washing process. These may be machine detergents characterizedby low sudsing action, or even all-purpose detergents exhibiting goodsudsing at temperatures up to 60 C. with the production of sudsdiminishing as the temperature rises above 60 C. In addition tosurfactant components, such detergents may simultaneously contain foamstabilizers and foam inhibitors having an activity that depends directlyon the prevailing temperature. The surfactant components usuallycomprise synthetic anionic, zwitterionic and/or non-ionic surfactantsand soaps having, for example, 12 to 18 carbon atoms in their fatty acidradicals or in the free fatty acids corresponding to the soaps. Thesurface active sulfonates are of particular practical importance assynthetic anionic surfactants, as are the corresponding sulfates. Theanionic surfactant component usually amounts to 50% of the entiresurfactant content as has been set out above.

The sudsing ability of anionic and/or non-ionic surfactants can becontrolled by the selection of appropriate fatty acid components. Thesuds inhibition, especially at elevated temperatures of from 60 to C.,increases with the carbon number and with the degree of saturation ofthe fatty acid radical. A powerful suds inhibition is realized withsynthetic anionic, zwitterionic or non-ionic surfactants bysaponification from fatty acid mixtures consisting of at least 50% offatty acids having 16 to 30 carbon atoms and at least 3%, and preferablyof more than 5%, of fatty acids having 20 and more carbon atoms, whereinthe saturated fatty acids containing at least 16 carbon atoms amount toat least 50% of the total soap content. The content of soap can beeliminated, or alternatively, can be replaced by synthetic wash-activesubstances, providing that the detergent composition contains other sudsinhibiting substances, such as hereinafter set out.

Where the complete detergent in accordance with the invention contains,in addition to the surfactant combination, neutral to alkaline reactingbuilder materials, the quantity thereof usually ranges between 0.5 and 7times, and preferably between 1 and 5 times the surfactant combination.Preferably, enough alkali is present in the latter builder materials sothat a 1% solution of the finished detergent has a pH ranging from 8 to12, and preferably from in the range of 9 to 11.

The composition of the complete detergents which are of particularpractical importance are set out by the following ranges of components:

8-50, and preferably 12 to 30 wt. percent of a surfactant combination,containing:

-90, and preferably 25-70 wt.-percent of a surfactant of the sulfonateor sulfate type.

0-90, and preferably 540 wt.-percent of a non-ionic surfactant.

0 90, and preferably 10-50 wt.-percent soap.

10-80, and preferably 30-70 wt.-percent of a textile softener.

0-6, and preferably 0.5-3 Wt.-percent of a foam stabilizer.

08, and preferably 0.5-5 wt.-percent of a foam inhibitor, preferably anon-surface active foam inhibitor,

20-89, and preferably 40-85 Wt.-percent of builder substances, at leasta portion of this component reacting alkalinely; the quantity of thealkaline and neutral reacting builder substances amounting preferably tofrom 0.5 to 7 times, and most preferably to from 1 to 5 times, the totalwash-active substance.

3-30 wt.-percent of other detergent components, such as bleachingcomponents and water.

The anionic, zwitterionic or non-ionic surfactants present in thesurfactant combinations or detergents according to the invention containin their molecules at least one hydrophobic radical having 8 to 30carbon atoms and one anionic or non-ionic water-solubilizig group. Thehydrophobic radical may be of an aliphatic or alicyclic, saturated orunsaturated nature, and may be directly bonded to the water-solubilizinggroup or through an intermediate. The intermediate can be, for example,a benzene ring, carboxylic acid ester group, carbonamide group, ethyleneglycol radical or propylene glycol radical.

The hydrophobic radical is preferably an aliphatic hydrocarbon radicalhaving about 10 to 18 carbon atoms, variations from this preferrednumber being possible, depending on the nature of the surfactantinvolved.

Those soaps which are suitable for use as anionic washactive substancesare derived from natural or synthetic fatty acids, or, if desired, fromresinic or naphthenic acids.

Of the synthetic anionic surfactants, the sulfonates and sulfates are ofparticular practical importance.

The sulfonates include, for example, the alkylaryl sulfonates,particularly the alkylbenzenesulfonates. Aliphatic sulfonates are alsoof interest, such as those which can be obtained, for example, frompreferably saturated hydrocarbons containing 8 to 18 and preferably 10to 16 carbon atoms in their molecules by 'sulfochlorination with sulfurdioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen,followed by conversion of the products thus obtained to thecorresponding sulfonates. Furthermore, mixtures of alkenesulfonates,hydroxyalkenesulfonates and hydroxyalkanesulfonates, such as thoseobtained, for example, from terminal or non-terminal C to C olefins bysulfonation with sulfur dioxide followed by acid or alkaline hydrolysisof the sulfonation products, can serve as aliphatic sulfonates. In thealiphatic sulfonates thus obtained, the 'sulfonate group is oftenpositioned on a secondary carbon atom. However, by utilizing thereaction of terminal olefins with bisulfite, it is possible to preparesulfonates having a primary, i.e., terminal sulfonate group.

The sulfonates which may be used according to the invention includeesters formed by reacting ot-sulfofatty acids with monovalent orpolyvalent alcohols containing 1 to 4 and preferably 1 to 2 carbonatoms.

Illustrative of the surfactants of the sulfate type are the fattyalcohol sulfates, particularly those derived from coconut fattyalcohols, tallow fatty alcohols or from oleyl alcohol. Sulfonationproducts of the sulfate type which can be used according to theinvention can also be prepared from terminal or non-terminal C to Colefins. This group of surfactants also includes sulfatized fatty acidalkylolamides, sulfatized monoglycerides and sulfatization products ofethoxylated and/or propoxylated fatty alcohols, alkyl phenols having 8to 15 carbon atoms in their alkyl radicals, fatty acid amides, fattyacid alkylolamides, etc., 0.5 to 20 moles, preferably 1 to 8 moles andpreferably 2 to 4 moles of ethylene and/or propylene oxide can be addedto one mole of the afore-mentioned ethoxylated and/or propoxylatedcompounds.

Instances of other usable sulfonates, include, the fatty acid esters ofoxyethanesulfonic acid and of dioxypropanesulfonic acid, as well as'thefatty acid amides of aminoethanesulfonic acid.

The detergent compositions according to the invention may also containsurface active synthetic carboxylate's, such as for example, the fattyacid esters or fatty alcohol ethers of hydroxycarboxylic acids and thefatty acid amides of aminocarboxylic acids such as glycocol orsarcosine.

The non-ionic surfactants which are hereinafter referred to asnon-ionics include products, the solubility of which in water isattributable to the presence of polyether chains, a-minoxide, sulfoxideor phosphinoxide groups, alkylolamide groupings, and generally, to anaccumulation of hydroxyl groups.

Of particular practical interest are the products which are obtained bythe addition of ethylene oxide and/or glycide onto fatty alcohols,alkylphenols, fatty acids, fatty amines, fatty acid amides and sulfonicacid amides. The'se non-ionics contain from 4 to 100, preferably 6 to40, and most preferably 8 to 20 ether radicals, and in particularethylene glycol ether radicals, per molecule. Further, propylene orbutylene glycol ether radicals may also be present in these polyglycolether radicals or terminally located thereon.

The non-ionics still further include the Water-insoluble polypropyleneglycols which have been made Water-soluble by the addition thereto ofethylene oxide and are well known by the tradenames Pluronics andTetronics" and also the products of the addition of propylene oxide ontoalkylene diamines or lower aliphatic alcohols containing l to 8 andpreferably 3 to 6 carbon atoms, known by the commercial name UnconFluid.

Suitable as non-ionics are also the fatty acid or sulfonic acidalkylolamides, which are derived, for example, from monoordialkylolamine, from dioxypropylamine or from other polyoxyalkylamines,such as the glycamines. They can be replaced by amides prepared fromhigher primary or secondary alkylamines and polyhydroxycarboxylic acids.

As aminoxides, the non-ionics derive from higher tertiary amines havingone hydrophobic alkyl radical and two shorter alkyl and/0r alkylolradicals containing up to 4 carbon atoms each have proved to be ofparticular interest.

The sudsing ability of the detergents according to the invention can beincreased or diminished by appropriate combinations of the differentsurfactants. Thus for example, the addition products of propylene oxideand the above-described polyethylene glycol others are characterized bya low sudsing capacity. By varying the number of ethylene glycol andpropylene glycol radicals present in the molecule, products can beobtained having very varied turbidity points. These non-ionics act assuds inhibitors on other non-ionics at temperatures above theirrespective turbidity points. As a result, they can be used in thesurfactant combinations according to the invention together with othernon-ionics and they can also be used in combination with othersurfactants, as non-ionic component, for example, in the previouslymentioned combinations of sulfates and/or sulfonates, soaps andnonionics.

The detergents, however, may also contain suds inhibitors which are notsurfactants. These include, for example, hydrocarbons of high molecularweight, such as paraffin, fatty acid esters, for instance, fatty acidtriglycerides, or fatty acid esters of monovalent alcohols, etc. Thesefoam inhibitors have a good effect, particularly in combinations of soapand surfactants of the sulfonate type.

Products of the reaction of cyanuric chloride with two or three moles ofa primary or secondary amine containing 1 to 24 carbon atoms, haveproven to be of particular practical importance. The tri tohexa-alkylmelamines or dito tetraalkyldiaminechlortriazines thuslyobtained have a remarkably broad spectrum of activity which isindependent of the type of surfactant involved, so that they are verywell suited, either alone or in combination with one another or incombination with the I previously mentioned foam inhibitors, forsuppressing the sudsing activity of surface active sulfates orsulfonates, soaps, zwitterionic or non-ionic wash-active substances,independently of whether the surfactant or surfactant combinationinvolved has of itself a low or high sudsing capacity.

The action of these suds inhibitors is temperature-dependent, andusually starts at a point within the melting range of the sudsinhibitor. This provides an additional way of adapting thetemperature-dependence of the dctergent to the requirements of practice.

The surfactant combinations of the invention can be marketed as such,for use in conjunction with wash alkalies, complex formers and otherconventional components used in the washing medium by commerciallaundries. However, the surfactant combinations can also be combinedwith these conventional detergent additives to make a ready to uselaundry detergent or laundry aid.

Of the conventional detergent additives, the watersoluble condensedphosphates, particularly the pyro-, trior tetrapolyphosphates are ofspecial practical importance.

They can be replaced by the known organic complex formers oralternatively can be combined with them.

The latter include, for example, nitrilotriacetic acid,ethylenediaminetetracetic acid, N-oxycthylethylene-diaminetriaceticacid, polyalkylene-polyamine-N-polyacetic acids and other known organiccomplex forming agents, it also being possible to use combinations ofdifferent complex formers. As illustrative of the other known complexformers, there may be mentioned the diand polyphosphonic acids havingthe following formulae:

no on HO OH and x on l it ou wherein R represents alkyl and R alkylenehaving 1 to '8, preferably 1 to 4, carbon atoms, and X and Y representhydrogen or alkyl having 1 to 4 carbon atoms. Carboxymethylcnephosphonicacid (HOOCCH PO(OH) can also be used according to the invention as acomplex former. The aforesaid complex formers can all be present as freeacids, but preferably are employed as their alkali salts.

In place of the condensed phosphates, or instead of the complex formers,or in combination with the latter, alkali reacting builder materials canbe present in the detergents according to the invention. These includesuch materials as the carbonates, bicarbonates or silicates of thealkalis. Neutrally reacting inorganic or organic salts can also beincorporated into the detergent compositions as, for example, the alkalisalts of sulfuric acid, benzene, toluene-, naphthaline-sulfonic, orsulfobenzoic or sulfoacetic acid or the salts of sulfodicarboxylicacids.

The detergents according to the invention are used preferably as whitelaundry detergents at boiling temperatures erably as white laundrydetergents at boining temperature or close to boiling temperature.Therefore they advantageously are formulated to contain a bleachingcomponent based on active oxygen or active chlorine.

Bleaches on the basis of active oxygen include the in organic percompounds, such as perpyrophosphates, perpolyphosphates, percarbonatesand perborates. Commercial sodium perborate having the approximatecomposition NaBO -H O -3H O is of particular practical importance. Inplace of the latter, perborates can be used which are partially orcompletely dehydrated, i.e., dehydrated down to the approximatecomposition NaBO -H O Further, NaBO -H O borates containing activeoxygen can be used, in which the ratio of Na O to B 0 is less than 0.5l, and preferably ranges from 0.4 to 0.15:1, and in which the ratio of H0 to Na ranges from 0.5 to 4:1. These products are described in GermanPat. 901,287 and in US. Pat. No. 2,491,789.

As illustrative of the active chlorine compounds that can be used asbleaching agents in the detergent compositions of the invention, thereare included compounds of both an inorganic and organic nature. Theinorganic active chlorine compounds include alkali hypochlorites, whichare preferably used in the form of their mixed salts or of compoundsformed by addition onto orthophosphates or onto condensed phosphates,such as pyroand polyphosphates, or alkali silicates. If the detergentcompositions and washing aids contain monpersulfates and chlorides,active chlorine forms in aqueous solution.

As organic active chlorine compounds there are preferably used theN-chlorine compounds in which one or two chlorine atoms are bonded to anitrogen atom, the third valence of the nitrogen atom being preferablyjointed to a negative group, as for instance, to a CO' or group. Thesecompounds include dichloroand trichlorocyanuric acid, chlorinatedalkylguanide or alkylbiguanides, chlorinated hydantoins and chlorinatedmelamines.

The detergent compositions can furthermore contain stabilizers for thebleaching component, and particularly for the per compounds if the sameare present. Often the complex formers as set out above have astabilizing action.

,However, other types of stabilizers may be present in their stead ortogether with them, as for example, those stabilizers acting as such byvirtue of their large surface area. Such stabilizers include, forexample, the silicates of magnesium or tin. Water-insoluble stannic acidcan also be used as a stabilizer.

The action of the bleaching components and primarily of the percompounds can be promoted by activators as known in the prior art. Theseinclude small quantities of heavy metal ions, particularly copper ions,which are present, preferably in the form of mixed silicates ofmagnesium.

Dirt carriers may also be contained in the detergents of the invention.The latter act to keep the dirt which is removed from the fibers in theWashing suspended in the Wash water and thereby preventing graying.Water-soluble colloids, usually of an organic nature, are suitable forthis purpose, such as for example, the water-soluble salts of polymericcarboxylic acids, glue, gelatine, salts of ether carboxylic acids, andether sulfonic acids of starch or cellulose, and salts of acid sulfuricesters of cellulose or starch. Water-soluble polyamides containing acidgroups are also suitable for this purpose. Starch can also be used ascan, starch products other than those named above, such as for example,decomposed starch, aldehyde starches, etc. Polyvinylpyrrolidone is alsosuitable for use as a dirt carrier.

The enzymes which are suitable for use in accordance with the inventioncan be derived from animals, microorganisms (such as bacteria or fungi)and plants, and particularly from digestive ferments, yeasts andbacteria strains. Generally they are composed of a mixture of differentenzymatic agents of complex composition. Such compositions are calledproteases, carbohydrases, esterases, lipases, oxidoreductases,catalases, peroxidases, ureases, isomerases, lyases, transferases,des-molasses or nucleases, according to the nature of their action. Theenzymatic agents obtained from bacterial strains or fungi, such asBacillus subtilis and Streptomyces griseus have proved to be ofparticular advantage. Instances of other usable enzymes are pepsin,pancreatin, trypsin, papain and diastase. The enzyme preparationsderived from Bacillus subtilis, however, have the advantage over thelatter enzymes in that they are relatively resistant to alkali, percompounds and anionic Wash-active substances, and are not appreciablyinactivated even at temperatures between 45 and 70 C. Their relativelgreat stability against oxidizing agents is based possibly on the lowcontent of free sulfhydryl groups.

The enzymes are marketed by the manufacturers usually in preparations towhich cutting agents have been added. Sodium sulfate, sodium chloride,alklai ortho-, pyroor polyphosphates, particularly tripolyphosphate, aresuitable as cutting agents. Often the still moist enzyme preparationsare combined with calcined salts, which then bind the water ofcrystallization that may be present in the enzymatic agent, whileagglomerating the particles into larger particles if desired.

If the enzymatic agents are available as dry products, it is possible touse the non-ionic organic compounds in liquid or paste form, such asethylene glycol, polyethylene glycols, butylene glycol or polybutyleneglycols and the known surfactants in liquid to paste form which areobtained, for example, by addition of ethylene oxide and, if desired,propylene oxide onto the starting materials used for the production ofsuch products, for the purpose of binding the enzymatic agent to thepreparation that is to be made in each case. For this purpose, a mixtureof the components of the surfactant combination or detergent compositionand the enzymatic agent is sprayed together with the non-ionic or theenzymatic agent is dispersed in the said non-ionic substances and thisdispersion is combined with the remaining components of the composition.If the balance of the components of the composition are solids, thedispersion of the enzymatic agents in the non-ionic components can besprayed onto these solid components.

If textiles, particularly those on a basis of cotton, which have beensoiled with proteinic, starchy and/ or oily stains,

are washed with the surfactant-softener-enzyme combinations according tothe invention or with the detergent compositions according to theinvention, the enzymes which they contain bring about a more rapidremoval of the stains, even at relatively low temperatures, particularlywhen the stains consist of dried blood, pus, gravy, etc. The textilesofteners contained in the products of the invention can then act on thetextiles at a relatively early point in the washing process. In thismanner a combined action of the enzymes and of the textile softeners isachieved.

If it is desired to market, not the final detergents, butsurfactant-softener combinations having an enzyme content, this is quitepossible. The formulas for such enzymecontaining surfactant-softenercombinations can easily be obtained from the above examples byeliminating the builder materials (from CMC to perborate, as Well assuch components as the dye and perfume). Nevertheless, it is possible toincorporate into the surfactant-softenerenzyme combinations buildermaterials in small amounts and also such substances as dirt carriers(CMC), complex formers (EDTA) and brightening agents.

The invention is illustrated but not limited to, by the followingexamples.

The following glycamides have proven to be suitable for use as textilesoftening agents in the surfactant-softening agent combinationsaccording to the invention and in the detergent compositions or washingaids containing them. In a number of the compounds the radicals R1\-and/or R CO' are derived from fatty acid mixtures of natural origin. Theunsaturated fatty acids contained in these fatty acid mixtures weresaturated to a substantial degree in the course of the process of theirmanufacture. The radicals R -CO however, are of the same degree ofsaturation as the fatty acid mixtures from which they are derived.

(a) Glucamide 1= 12 25 2= rl a5 Total 29 C atoms Glucamide r= 14 29 2 l531 Total 29 C atoms Glucamide r= 1e a3 2= 11 23 Total 27 C atomsGlucamide 1= 1a si R2:C'1H15 Total 25 C atoms Glucamide R1'=C36H6OC16H332= 15 a1 Total 34 C atoms Glucamide R =C to C mixture from coconut fattyacid, avg.

approx. C R =C to C mixture from tallow fatty acid, avg.

approx. C

Total approx. 29 C atomn Glucamide R =C to C mixture from tallow fattyacid, avg.

approx. C R =C to C mixture from coconut fatty acid, avg.

approx. C

Total approx. 30 C atoms Fructamide R =C to C mixture from coconut fattyacid, avg.

approx. C R :C to C mixture from tallow fatty acid, avg.

approx. C

Total approx. 29 C atoms (i) Glucamide mixture from invert sugar R =C toC mixture from coconut fatty acid, avg.

approx. C

Rg=C to C mixture from tallow fatty acid, avg.

approx. C

Total approx. 29 C atoms (j) Glucamide mixture from invert sugar R =C toC mixture from tallow fatty acid, avg.

approx. C R =C to C mixture from coconut fatty acid, avg.

approx. C

Total approx. 29 atoms In the following examples there are described thecompositions of a number of surfactant-softener combinations accordingto the invention and of a number of detergents containing suchsurfactant-softener combinations. The following terms which are used inexamples are defined as follows:

ABS-represents the salt of an alkylbenzenesulfonic acid obtained bycondensing straight-chained olefins with benzene and sulfonating thealkylbenzene thus produced; the resulting alkylbenzen'e sulfonate havingto 15 and preferably 11 to 13, carbon atoms in its alkyl chain.

Olefin sulfonate-designates a sulfonate (usually 12-16 carbon atoms)obtained by sulfonating a straightchained terminal or non-terminalolefin with 50;; and thereafter hydrolyzing the sulfonation product withlye. It is comprised essentially of alkenesulfonate andhydroxyalkanesulfonate, but also contains small amounts of disulfonates.

Oleyl alcohol-+10 EO--Coconut alcohol+ EO Nonylphenol+9.5 or +60 E0 asthe case may beidentify products formed by the addition of the statedamount of ethylene oxide onto the hydroxyl compounds named (coconutalcohol=an alcohol made from coconut fatty acid).

Coconut alcohol+9 EO'+12 PO--represents a product formed by the reactionof 12 moles of propylene oxide with a product of the addition of 9 molesof ethylene oxide onto 1 mole of a coconut alcohol.

Fatty acid monoethanolamide+8 EOrepresents a product formed by theaddition of 8 moles of ethylene oxide onto 1 mole of monoethanolamideprepared from coconut fatty acid.

The composition of the fatty acid mixtures from which the various soapscontained in the surfactant combinations or detergent compositions arederived can be seen in the following table:

TABLE I.-COMPOSITIONS OF THE FATTY ACID MIXTURES CO RRESPONDING TO THESOAPS Unless otherwise stated, the anionic surfactants and other saltsare present in the form of their sodium salts. All percentages arepercentages by weight.

In the examples, the suds inhibitor is associated with the surfactantcombination. This is incorrect, insofar as the special suds inhibitorsmentioned in the description of the invention are not to be consideredas surfactants. They are nevertheless listed together with thesurfactant combination because they certainly affect the sudsing abilityof the surfactants. In the preparation of the detergent compositions thesuds inhibitor used in each case was dissolved in a suitable organicsolvent or motten and sprayed by means of a nozzle onto the movingsurfactant combination or detergent which was in powder form. Wheresurfactant combinations containing synthetic sulfates or sulfonates inadmixture with soap are involved, parafiin or paraffin oil, for example,is suitable for suds inhibitor. In the case of the surfactantcombinations described, an N-N'-N"-trialkylmelamine was used as the sudsinhibitor. Equally good results were obtained when this suds inhibitorwas replaced by a bis-(alkylamino)- monochlortriazine or with a mixtureof 10 to of the melamine derivative and 90 to 10% of the chlortriazinederivative. In all of these triazine derviatives, the alkyl radicalswere in the form of mixtures of homologs having from 8 to 18 carbonatoms. The suds inhibiting action set in at temperatures of about 50 C.and reached its full extent at temperatures above 65 C.

The following Examples 1 to 8, describe various surfactant combinationscontaining percentages of the textile softening agents according to theinvention.

Example 1(a) Percent ABS 42 Oleyl alcohol+l0 EO 14 Soap E 6 Textilesofteners (a-j) 38 Examples 1(b) and (c) In the surfactant combinationaccording to Example 1(a), (b) 25% of the weight of the ABS was replacedby olefin sulfonate (c) all of the ABS was replaced by alkane sulfonate.Products that were similarly usable were obtained in each instance.

Example 2 Percent ABS 37 Oleyl alcohol+l0 EO l7 Textile softeners (aj)46- Example 3 Percent ABS 44 Oleyl alcohol+ 10 E0 14 Soap D 4 Textilesofteners (a-j) 38 Example 4 Percent ABS -1 34 Fatty acid ethanolamide+8EO 13 Soap C 20 Textile softeners (a-j) 33 Example 5 Percent Coconutfatty alcohol+20 E0 48 Coconut fatty alcohol+9 EO+12 PO 25 Textilesofteners (a-j) 27 Example 6 Percent ABS 49 Oleyl alcohol-H0 EO l6Textile softeners (a-j) 33 Suds inhibitor 2 Example 7 Percent Olefinsulfonate 32 Oleyl alcohol+10 E0 i 16 Soap A 15 Textile softeners (a-j)34 Suds inhibitor s-....---..--..-...--........... 3

13 Example 8 Percent Olefin sulfonate 32 Oleyl alcohol-l-IO EO 16 Soap Bt 14 Textile softeners (a-j) 34 Suds inhibitor 4 The following examplesdescribe a number of detergents which cont-ain combinations of basicmaterials in addition to the surfactant combinations according toExamples 1 to 8.

Example 9 Percent Surfactant combination per Examples 1-8 19 Na P O1 45Na O-3.3SiO 4.5 MgSiO v i 1.0 CMC 1.5 N3BOZHZOZ'3HZO Rest: Brighteners,perfume, sodium sulfate and wate Example Percent Surfactant combinationper Examples l-8 20.8 Nil-51 301 Y N3203.3Sl02 MgSiO 2.5 CMC 0.8 NaBO -HO -3H O 31.3

Rest: Brighteners, perfume, sodium sulfate and water.

Example 12 Percent Surfactant combination per Examples 1-8 19.5Nitrilotriacetate 19.0 Hydroxyethanediphosphonate 14.0 Na P O NaBO-33SiO 4.5 MgSiO n 1.0 CMC 1.5 NaBO 'H O -3H O 16.0

Rest: Brighteners, perfume, sodium sulfate and water.

Rest: Brighteners, perfume, sodium sulfate and water.

14 Example 15 Percent Nonylphenol+60 E0 12.0 Soap D 4.0 Textile softener(f) 20.0 Sodium hexametaphosphate 40.0 Na O'-3.3SiO 4.0 MgSiO 2.4 CMC1.6 NaBO2'H2O '3H2O Rest: Brighteners, perfume, sodium sulfate andwater.

Same composition as in (a), but with only 10% textile softener (f).

Example 16 Percent Sodium salt of a methylesterified a-sulfofatty acidfrom hydrogenated tallow 12.0 Soap E 4.0 Textile softener (f) 20.0Sodium hexametaphosphate 40.0 Na o-assio 4.0 MgSiO 2.4 CMC 1.6

'NaBO H202 Rest: Brighteners, perfume, sodium sulfate and water.

0 Same composition as (a), but with only 10% textile softener (f).

Example 17 Percent Olefin sulfonate from C -C olefin 12.0 Soap D 4.0Textile softener (f) 20.0 Sodium hexametaphosphate 40.0 Na O-3.3SiO 4.0MgSiO' 2.4 CMC 1.6

NaBO3'H202'3H2O Rest: Brighteners, perfume, sodium sulfate and water.

The detergents of Examples 9 to 12 and 14 to 17 contain sodium perboratetetrahydrate as the bleaching component. This can be replaced wholly orpartially by other per compounds, such as those mentioned in thedescription of the invention. lActive chlorine compounds can be usedinstead of the per compounds. If no value is placed on the bleachingcomponent it can be eliminated all together along with the magnesiumsilicate serving as its stabilizer. In such cases the percentages of thebleaching component and magnesium silicate are replaced by increasingthe percentages of the other components proportionally, unless it isdesired, for special reasons, to increase the percentage of a certaincomponent, such as the surfactant, the textile softener or the buildermaterial by that amount.

If terrycloth is washed in a drum-type Washing machine under the usualconditions, using the described detergents, the fabric is fluffy afterdrying and has a softer feel than when it is washed using a detergent ofthe same composition in which the textile softener has been replaced bythe same amount of sodium sulfate. The difference in the compressibilityand in the feel of the fabric becomes more apparent after severalwashings.

:Detergent compositions were prepared in the conventional manner, with acomposition that differed from those of Examples 9 to 17 only in thatthey also contained enzymes. For this reason, only the quantities of theenzymes are now set out it being possible, depending on the desiredeffect, to add any enzyme or any enzyme combination in accordance withthe invention to any of the detergent compositions described in theabove examples. The enzymes which were employed were the commerciallyavailable products which had been adjusted to the following activitiesby the manufacturer by adding sodium sulfate in quantities of about 7 to15%:

A protease having 125,000 LVE/g. An amylase having 75,000 SKBE/ g. Alipase having 10,000 IE/ g.

In addition to the quantity of enzyme utilized, the enzyme activity isset out in the examples, with reference to one gram of detergent.

The suds inhibitors were incorporated into the detergents compositionsin the same manner as described above or alternatively they were mixedin the form of fine powders with the detergent. If they were sprayed on,the suds inhibitors were fixed to the solid particles of the preparationor to a solid component of the preparation; it is even possible thatthey wholly or partially envelop the said particles.

(A) A detergent composition according to Examples 9-17 containing0.3-1.5 wt. percent protease (375-1875 LVE/g.).

(B) A detergent composition according to Examples 9-17 containing 1.2wt. percent lipase (120 IE/g.).

(C) A detergent composition according to Examples 9-17 containing 0.4wt. percent protease (500 LVE/g.) and 1.0 wt. percent amylase (750SKBE/g.).

(D) A detergent composition according to Examples 9- 17 containing 2.0wt. percent amylase (1500 SKBE/g.).

(E) A detergent composition according to Examples 9- 17 containing 0.2wt. percent protease (250 LVE/ g.) and 0.5 wt. percent amylase (375SKBE/g.) and 0.5 wt. percent lipase (50 IE/g.).

(F) A detergent composition according to Examples 9- 17 containing 1.0wt. percent protease (1250 LVE/g.) and 0.3 wt. percent amylase (225SKBE/g.) and 0.4 Wt. percent lipase (4O IE/g.).

What is claimed is:

1. A detergent composition consisting of to 90 wt. percent of at leastone member selected from the group consisting of anionic, zwitterionicand non-ionic surfactants and 10 to 80 wt. percent of a textilesoftening N- alkyl-N-acyl-N-polyhydroxyalkyl compound having theformula:

R NC O-R;

wherein R is (1) alkyl or alkenyl of 10 to 22 carbon atoms, or (2) alkylor alkenyl of 10 to 22 carbon atoms with an ether oxygen linkage betweeneither the 2 and 3 or 3 and 4 carbon atoms from the nitrogen atom,

R is alkyl or alkenyl of 7 to 21 carbon atoms,

R +R have 23 to 39 carbon atoms, and

Z is (1) -CH (CHO'H) CH OH or (2) -CH (CH OH) (CHOHhCHgOH 2. Thecomposition according to claim 1 wherein R has 12 to 20 carbon atoms, Rhas 11 to 19 carbon atoms,

16 R -l-R have a total of 27 to 35 carbon atoms, and wherein of 100parts of the combination of said surfactants and saidN-alkyl-N-acyl-N-polyhydroxyalkyl compound, 30 to parts thereof consistof the latter.

3. A composition according to claim 1, wherein said anionic surfactantgroup member is present in an amount of at least 50% of the totalquantity of surfactants present.

4. A composition according to claim 1, additionally containing at leastone detergent builder.

5. A composition according to claim 4, wherein the mixture ofsurfactants and the textile softening compound is present in an amountof from 5 to Wt. percent and said builder substances are present in anamount of from 20 to 95 wt. percent.

6. A composition according to claim 4, additionally containing an activeamount of an enzyme selected from the group consisting of the proteases,carbohydrases, esterases, lipases, oxidoreductases, catalses,peroxidases, ureases, isomerases, lyases, transferases, desmolases ornucleases.

7. The composition of claim 6, wherein said enzyme is elected from thegroup conisting of:

protases 62.5 to 50,000 LVE/ g. of total composition,

amylases 25 to 50,000 SKBE/g. of total composition,

and

lipases 2.5 to 10,000 IE/g. of total composition.

8. A composition according to claim 4, wherein said mixture ofsurfactants and textile softening compound is present in an amount offrom 8 to 50 wt. percent and comprises:

0 to wt. percent of a member selected from the group consisting ofanionic sulfonates and sulfates,

0 to 90 wt. percent of non-ionics,

0 to 90 wt. percent of soap, and

10 to up to 80 wt. percent of said textile softening compound, andwherein said builder substances are present in an amount of from 20 to89 wt. percent.

9. A method for washing and softening a textile-fabric articlecomprising laundering said article in water containing dissolved thereina detergent composition according to claim 1.

References Cited UNITED STATES PATENTS LEON D. ROSDOL, Primary ExaminerD. L. ALBRECHT, Assistant Examiner US. Cl. X.R. 252-88, 132, 137, 152;260-404 0 UNl'JIrlI.) s'rlx'l xcs PA'JICN'L omen CERTIFICATE OFCORRECTION Patent No. 3,654, 166 Dated April 4, 1972 Inv nt Hans-WernerEckert. e15 al It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected. as shovm below:

line 5 "Postfach" iri the address should have been omitted line 68"laundering" should be --laundered- Col. 2 line 25 "compounds" should be--compound-- I line 5 1' "etherally" should be --'ethereally-- line 72 II "deterents" should be --deterg-ents- .1

Col. 3, line 5 after "amylases" insertend lipases-- Col. 3 line 40"usuable" should be --usable-- line 66 "Physioloische" should. be--Physiologische'- Col. 4, line 2 "monosacchardies" should be--monosaccharides-- lirie 6 "process" should be --processed-- line 32ihserta comma after "palm'oil" Col. 5, line 39 I "water-solubilizig" Ishould -be --water-solubilizing-- UNI'JEI) 5131'11-35 lfAfl'l'lN'lOFFICE. .(lE R llFlCj-l'lli OF CORRECTION P666116 116. 3,654,166 DatedApril 4, 1972 I fl' Hans-Werner Eckert, et al It is certified that errorappears in thcabovcidcntiied patent and that said Letters Patent are.hereby corrected as shoym below:

061. a, line 28 4 "temperatures" should be temperature-- line 29 cancelin its entiisety line 61 I "j ointed" should be -j oined- -c61.'10,-line 52 "C H 0C H should be C H 00 H line 60 6 "29 C atomn" should be--29 C atoms" line 67 1 f "(h) Fructamide" should be --(h) Glucamide-'-Col. ll -line 58 in the Table, under the heading "C"; 5th, item,

"3" should be --l3-- Col. 13 line 26 6 4 Na 0,3,3Si0 should be -'-MgSi03.3 8-1.0

- 2 .2 4 A 3 2 C01. 16 line 18 v f "'catal'ses" should-'be c'atalases vline 21 V "eleqtted'l should be --selected line 22' "protases" should be--p'roteases-- Pz ltcnt No. 3 654 166 Dntcd A ril 4-, 1972 -Invcntor( s)Hans-Werner Ecker-fi, et a1 If is certifiedthat error appears in theabove-identifiedpatcnb and that said Letters Patent are hereby correctedas shown below:

Col. 16, line 53 4 1 the reference to British patent '7 l l,423; 5/ l957 shuld be 771,423 4/1957" 7 Signed and sealed this 10th day ofOctober 1972.

(SEAL) Attest; I

EDWARD M.FLETGHER,JR; ROBERT GOTTSCHALK.

-Attesting Officer 7 Commissioner of Patents

